EP3556807A1 - Composition de résine polymère à cristaux liquides pour plaque externe et plaque externe - Google Patents

Composition de résine polymère à cristaux liquides pour plaque externe et plaque externe Download PDF

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Publication number
EP3556807A1
EP3556807A1 EP17881959.5A EP17881959A EP3556807A1 EP 3556807 A1 EP3556807 A1 EP 3556807A1 EP 17881959 A EP17881959 A EP 17881959A EP 3556807 A1 EP3556807 A1 EP 3556807A1
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EP
European Patent Office
Prior art keywords
outer plate
liquid crystal
crystal polymer
resin composition
gate
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EP17881959.5A
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German (de)
English (en)
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EP3556807A4 (fr
Inventor
Shintaro Komatsu
Taiga Sakai
Mitsuo Maeda
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of EP3556807A1 publication Critical patent/EP3556807A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D25/00—Superstructure or monocoque structure sub-units; Parts or details thereof not otherwise provided for
    • B62D25/02—Side panels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/26—Moulds
    • B29C45/27—Sprue channels ; Runner channels or runner nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0079—Liquid crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D25/00—Superstructure or monocoque structure sub-units; Parts or details thereof not otherwise provided for
    • B62D25/06—Fixed roofs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
    • B62D29/04—Superstructures, understructures, or sub-units thereof, characterised by the material thereof predominantly of synthetic material
    • B62D29/043—Superstructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/12—Polymer mixtures characterised by other features containing additives being liquid crystalline or anisotropic in the melt

Definitions

  • the present invention relates to a liquid crystal polymer resin composition for an outer plate and an outer plate.
  • Molded bodies for which a liquid crystal polymer (liquid crystalline resin) is used as a forming material have a high strength, high heat resistance, and high dimensional accuracy. Therefore, liquid crystal polymers are used as a forming material of electronic components having a relatively small size such as connectors or relay components (for example, refer to Patent Document 1). Molded bodies for which a liquid crystal polymer is used as a forming material are molded by injection molding.
  • Patent Document 1 Japanese Unexamined Patent Application, First Publication No. H07-126383
  • outer plates exterior components for electronic goods or vehicles
  • the present invention has been made in consideration of the above-described circumstance, and an object of the present invention is to provide a new liquid crystal polymer resin composition for an outer plate.
  • another object of the present invention is to provide an outer plate that is obtained using the liquid crystal polymer resin composition for an outer plate.
  • the present inventors found that, in the case of using a liquid crystal polymer as a forming material of an outer plate, the above-described objects can be achieved by producing the liquid crystal polymer as a composition with a plate-shaped filler and completed the present invention.
  • the present invention employed the following.
  • a liquid crystal polymer resin composition for an outer plate according to an aspect of the present invention includes a liquid crystal polymer and a plate-shaped filler.
  • the "outer plate” refers to an exterior component for electronic goods or vehicles (cars).
  • the liquid crystal polymer resin composition for an outer plate is used as a forming material of the outer plate.
  • the liquid crystal polymer resin composition for an outer plate of the present embodiment is molded to an outer plate by injection molding.
  • the liquid crystal polymer resin composition for an outer plate of the present embodiment can be used as a forming material of large-sized outer plates having a maximum surface with a projected area of 400 cm 2 or more.
  • the "projected area” is used as an index that indicates the dimensions (sizes) of the outer plate.
  • the dimensions of the outer plate can be converted to and expressed as the projected area (unit: cm 2 ).
  • the "projected area” refers to the area of the shape of the outer plate formed on a planar surface (criterion surface) perpendicular to the normal direction to the upper surface of the outer plate when a parallel light ray is radiated onto the upper surface in the normal direction.
  • the "maximum surface” refers to a surface that is determined as described below.
  • the projected areas of a plurality of surfaces that forms the three-dimensional shape of the outer plate are obtained.
  • the maximum area is regarded as the projected area of the curved surface.
  • the areas of individual images are compared with each other, and the surface showing the maximum value is regarded as the "maximum surface". It is needless to say that the maximum surface can be visually determined in a case where the outer plate is a simple cuboid.
  • the liquid crystal polymer resin composition for an outer plate of the present embodiment can be used as a forming material of outer plates having an average thickness of 0.03 cm or more and 0.5 cm or less.
  • the "average thickness” refers to a value obtained by measuring the thickness of the outer plate at a plurality of points and computing the arithmetic average thereof.
  • the “thickness” refers to a length from one surface to the other surface of the outer plate in the normal direction to a planar surface that is imaged to be in contact with a thickness measurement location in the outer plate.
  • a place which is provided with a specially different thickness in order to carry out a specific function such as, for example, a screw clamp is not selected as the measurement location. And the place is not an average structure that is intended to guarantee a function of the outer plate such a screw hole.
  • outer plates that are molded using the liquid crystal polymer resin composition for an outer plate of the present embodiment have an average thickness of 0.03 cm or more, the outer plates are durable to external forces that can be imagined for outer plates, which is preferable.
  • the average thickness of an outer plate that is molded using the liquid crystal polymer resin composition for an outer plate is preferably 0.03 cm or more since it is possible to suppress the resin pressure to be small enough for injection molding with the clamp capability of commercially available injection molders, which is preferable.
  • the average thickness of an outer plate is preferably 0.5 cm or less. Since the outer plate has a sufficient shape-holding force against external forces and has a weight that can be sufficiently reduced compared with the weight of an outer plate being formed using a metallic material, which is preferable.
  • the liquid crystal polymer resin composition for an outer plate of the present embodiment can be used as a forming material of outer plates in which the ratio of the projected area of the maximum surface (unit: cm 2 ) to the average thickness (unit: cm) is 8,000 or more.
  • the plate-shaped filler that is included in the liquid crystal polymer resin composition for an outer plate is arranged in an in-plane direction of the outer plate. And thus it can be expected that a synergetic effect for suppressing the warping of the outer plate, which is preferable.
  • the liquid crystal polymer that is used in the present embodiment has repeating units represented by General Formulae (1), (2), and (3) below.
  • Ar 1 is a phenylene group, a naphthylene group, or a biphenylene group
  • Ar 2 and Ar 3 each are independently a phenylene group, a naphthylene group, a biphenylene group, or a group represented by General Formula (4) below
  • X and Y each is independently an oxygen atom or an imino group
  • one or more hydrogen atoms in Ar 1 , Ar 2 , and Ar 3 each may be independently substituted with a halogen atom, an alkyl group, or an aryl group.
  • Ar 4 and Ar 5 each are independently a phenylene group or a naphthylene group; Z is an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group.
  • halogen atom capable of substituting for one or more hydrogen atoms in the groups represented by Ar 1 , Ar 2 , or Ar 3
  • a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are exemplary examples.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, and the like are exemplary examples.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10.
  • aryl group capable of substituting for one or more hydrogen atoms in the groups represented by Ar 1 , Ar 2 , or Ar 3 monocyclic aromatic groups such as a phenyl group, an o-tolyl group, an m-tolyl group, and a p-tolyl group and fused-ring aromatic groups such as a 1-naphthyl and a 2-naphthyl group are exemplary examples.
  • the number of carbon atoms in the aryl group is preferably 6 to 20.
  • the number of hydrogen atoms substituted is preferably one or two and more preferably one in each of the groups represented by Ar 1 , Ar 2 , or Ar 3 independently.
  • examples of the alkylidene group include a methylene group, an ethylidene group, an isopropylidene group, an n-butylidene group, a 2-ethylhexylidene group, and the like.
  • the number of carbon atoms in the alkylidene group is preferably 1 to 10.
  • repeating unit represented by General Formula (1) a repeating unit in which Ar 1 is a 1,4-phenylene group (a repeating unit derived from p-hydroxybenzoic acid) and a repeating unit in which Ar 1 is a 2,6-naphthylene group (a repeating unit derived from 6-hydroxy-2-naphthoic acid) are preferable, and a repeating unit in which Ar 1 is a 2,6-naphthylene group is more preferable.
  • 2-hydroxy-6-naphthoic acid, p-hydroxybenzoic acid, and 4-(4-hydroxyphenyl)benzoic acid are exemplary examples.
  • monomers having a benzene ring or a naphthalene ring in which a hydrogen atom is substituted with a halogen atom or an alkyl group or aryl group having 1 to 10 carbon atoms are also exemplary examples.
  • these monomers may be converted to an ester-forming derivative described below and then used as the monomer that forms the repeating unit represented by General Formula (1).
  • a repeating unit in which Ar 2 is a 1,4-phenylene group (a repeating unit derived from terephthalic acid), a repeating unit in which Ar 2 is a 1,3-phenylene group (a repeating unit derived from isophthalic acid), a repeating unit in which Ar 2 is a 2,6-naphthylene group (a repeating unit derived from 2,6-naphthalenedicarboxylic acid), and a repeating unit in which Ar 2 is a diphenyl ether-4,4'-diyl group (a repeating unit derived from diphenyl ether-4,4'-dicarboxylic acid) are preferable. Furthermore, as the repeating unit represented by General Formula (2), a repeating unit in which Ar 2 is a 1,4-phenylene group and a repeating unit in which Ar 2 is a 1,3-phenylene group are more preferable.
  • 2,6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, or biphenyl-4,4'-dicarboxylic acid is an exemplary example.
  • monomers having a benzene ring or a naphthalene ring in which a hydrogen atom is substituted with a halogen atom or an alkyl group or aryl group having 1 to 10 carbon atoms are also exemplary examples.
  • these monomers may be converted to an ester-forming derivative described below and then used as the monomer that forms the repeating unit represented by General Formula (2).
  • a repeating unit in which Ar 3 is a 1,4-phenylene group (a repeating unit derived from hydroquinone, p-aminophenol, or p-phenylenediamine) and a repeating unit in which Ar 3 is a 4,4'-biphenylene group (a repeating unit derived from 4,4'-hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl, or 4,4'-diaminobiphenyl) are preferable.
  • the monomer that forms the repeating unit represented by General Formula (3) 2,6-naphthol, hydroquinone, resorcinol, and 4,4'-hydroxybiphenyl are exemplary examples. Furthermore, as the monomer that forms the repeating unit represented by General Formula (3), monomers having a benzene ring or a naphthalene ring in which a hydrogen atom is substituted with a halogen atom or an alkyl group or aryl group having 1 to 10 carbon atoms are also exemplary examples. Furthermore, these monomers may be converted to an ester-forming derivative described below and then used as the monomer that forms the repeating unit represented by General Formula (3).
  • an ester-forming derivative is preferably used in order to facilitate polymerization in a process for manufacturing a polyester.
  • the ester-forming derivative refers to a monomer having a group that accelerates an ester-generating reaction. Specific examples thereof include highly reactive derivatives such as an ester-forming derivative in which a carboxylic acid group in the monomer molecule is converted to an acid halide or an acid anhydride or an ester-forming derivative in which a hydroxyl group in the monomer molecule is converted to a lower carboxylic acid ester group.
  • the amount of the repeating unit (1) in the liquid crystal polymer is preferably 30 mol% or more, more preferably 30 mol% or more and 80 mol% or less, still more preferably 40 mol% or more and 70 mol% or less, and particularly preferably 45 mol% or more and 65 mol% or less with respect to the total amount (100 mol%) of the repeating unit (1), the repeating unit (2), and the repeating unit (3).
  • the amount of the repeating unit (2) in the liquid crystal polymer is preferably 35 mol% or more, more preferably 10 mol% or more and 35 mol% or less, still more preferably 15 mol% or more and 30 mol% or less, and particularly preferably 17.5 mol% or more and 27.5 mol% or less with respect to the total amount (100 mol%) of the repeating unit (1), the repeating unit (2), and the repeating unit (3).
  • the amount of the repeating unit (3) in the liquid crystal polymer is preferably 35 mol% or more, more preferably 10 mol% or more and 35 mol% or less, still more preferably 15 mol% or more and 30 mol% or less, and particularly preferably 17.5 mol% or more and 27.5 mol% or less with respect to the total amount (100 mol%) of the repeating unit (1), the repeating unit (2), and the repeating unit (3).
  • the content ratio of the repeating unit (1) is 30 mol% or more and 80 mol% or less
  • the repeating unit (2) is 10 mol% or more and 35 mol% or less
  • the repeating unit (3) is 10 mol% or more and 35 mol% or less.
  • the liquid crystal polymer is likely to improve in melt fluidity, heat resistance, strength, and hardness.
  • the ratio of the amount of the repeating unit (2) to the amount of the repeating unit (3) is indicated by [the amount of the repeating unit (2)]/[the amount of the repeating unit (3)] (mol/mol) and is preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, and still more preferably 0.98/1 to 1/0.98.
  • the liquid crystal polymer respectively has repeating units including a 2,6-naphtylene group as the repeating unit (1), the repeating unit (2), and the repeating unit (3).
  • the amount of the repeating units including a 2,6-naphtylene group is 40 mol% or more with respect to the total (100 mol%) of all of the repeating units.
  • the amount of the repeating units including a 2,6-naphtylene group is 40 mol% or more, a liquid crystal polymer resin composition to be obtained becomes more favorable in fluidity during a melting process and becomes more suitable to a process of an electronic device chassis having a fine grid structure.
  • the number of each of the repeating units (1) to (3) in the liquid crystal polymer may be one or more independently.
  • the liquid crystal polymer may have one or more repeating units other than the repeating units (1) to (3), and the amount thereof is preferably 0 mol% or more and 10 mol% or less and more preferably 0 mol% or more and 5 mol% or less of the total of all of the repeating units.
  • the liquid crystal polymer preferably has, as the repeating unit (3), a repeating unit in which X and Y each are an oxygen atom, that is, a repeating unit derived from a predetermined aromatic diol since the melt viscosity becomes low.
  • the liquid crystal polymer more preferably has, as the repeating unit (3), only a repeating unit in which X and Y each are an oxygen atom.
  • the liquid crystal polymer is preferably manufactured by melt-polymerizing a raw material monomer that corresponds to the repeating unit configuring the liquid crystal polymer and solid-phase-polymerizing the obtained polymerized substance (prepolymer).
  • prepolymer a raw material monomer that corresponds to the repeating unit configuring the liquid crystal polymer and solid-phase-polymerizing the obtained polymerized substance (prepolymer).
  • the melt polymerization may be carried out in the presence of a catalyst.
  • metal compounds such as magnesium acetate, tin diacetate, tetrabutyl titanate, lead acetate, sodium acetate, and ammonium trioxide or nitrogen-containing heterocyclic compounds such as N,N-dimethylaminopyridine and N-methylimidazole are exemplary examples.
  • a nitrogen-containing heterocyclic compound is preferable.
  • the flow-starting temperature of the liquid crystal polymer is preferably 270°C or higher, more preferably 270°C or higher and 400°C or lower, and still more preferably 280°C or higher and 380°C or lower.
  • the liquid crystal polymer is more likely to improve in heat resistance, strength, and stiffness as the flow-starting temperature increases.
  • the flow-starting temperature of the liquid crystal polymer is too high, a high temperature is required to melt the liquid crystal polymer, and thus the liquid crystal polymer is likely to thermally deteriorate during molding or the viscosity increases during melting and thus the fluidity degrades.
  • the flow-starting temperature is also referred to as the flow temperature and is a temperature at which the liquid crystal polymer exhibits a viscosity of 4,800 Pa ⁇ s (48,000 poise) when melted while increasing the temperature at a rate of 4°C/minute under a load of 9.8 MPa (100 kgf/cm 2 ) and extracted from a nozzle having an inner diameter of 1 mm and a length of 10 mm using a capillary rheometer.
  • the flow-starting temperature of the liquid crystal polymer serves as a rough indication of the molecular weight of the liquid crystal polymer (refer to Koide Naoyuki's "Synthesis, molding, and application of liquid crystal polymers", CMC Publishing Co., Ltd., June 5, 1987, p. 95 ).
  • liquid crystal polymer resin composition for an outer plate of the present embodiment only one liquid crystal polymer may be used singly or two or more liquid crystal polymers may be jointly used.
  • the liquid crystal polymer resin composition for an outer plate in the present invention includes 20 parts by mass or more and 70 parts by mass or less of the plate-shaped filler with respect to 100 parts by mass of the liquid crystal polymer.
  • the liquid crystal polymer resin composition for an outer plate including the plate-shaped filler in the above-described range exhibits favorable fluidity at the time of forming an outer plate by injection molding. Therefore, the liquid crystal polymer resin composition for an outer plate in the present embodiment can be preferably used to manufacture outer plates that are film and demand injection molding in a broad range.
  • the plate-shaped filler is not easily oriented at the time of causing the molten resin to flow, and the flow of the resin is likely to be locally hindered. Therefore, at the time of injection molding using the liquid crystal polymer resin composition for an outer plate in the present embodiment, the flow of the molten resin is disarrayed in the vicinity of the plate-shaped filler. Therefore, the liquid crystal polymer is not easily oriented in the flow direction of the molten resin, and there is a tendency that the warping of the molded body attributed to the orientation of the resin does not easily appear.
  • talc As the plate-shaped filler, talc, mica, graphite, wollastonite, barium sulfate, calcium carbonate, and the like are exemplary examples.
  • the mica may be white mica, may be phlogopite, may be fluorine phlogopite, or may be tetrasilisic mica.
  • the amount of the plate-shaped filler is preferably 25 parts by mass or more with respect to 100 parts by mass of the liquid crystal polymer.
  • the amount of the plate-shaped filler is preferably 50 parts by mass or less and more preferably 35 parts by mass or less with respect to 100 parts by mass of the liquid crystal polymer.
  • the upper limit value and the lower limit value of the amount of the plate-shaped filler can be arbitrarily combined.
  • the liquid crystal polymer resin composition for an outer plate in the present embodiment may contain other components that correspond to neither the liquid crystal polymer nor the plate-shaped filler as long as the effect of the present invention is not impaired.
  • a filler other than the plate-shaped filler an additive, a resin other than the liquid crystal polymer, and the like are exemplary examples.
  • the filler other than the plate-shaped filler may be a fibrous filler or a particulate filler.
  • the filler other than the plate-shaped filler may be an inorganic filler or an organic filler.
  • the fibrous inorganic filler glass fibers; carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers; ceramic fibers such as silica fibers, alumina fibers, and silica alumina fibers; and metal fibers such as stainless steel fibers.
  • whiskers such as potassium titanate whiskers, barium titanate whiskers, wollastonite whiskers, aluminum borate whisker, silicon nitride whiskers, and silicon carbide whiskers are also exemplary examples.
  • glass fibers manufactured using a variety of methods such as chopped glass fibers and milled glass fibers are exemplary examples.
  • the carbon fibers PAN-based carbon fibers for which polyacrylonitrile is used as a raw material, pitch-based carbon fibers for which coal tar and petroleum pitch is used as a raw material, cellulose-based carbon fibers for which viscose rayon, cellulose acetate, or the like is used as a raw material, vapor-grown carbon fibers for which a hydrocarbon or the like is used as a raw material are exemplary examples.
  • the carbon fiber may be a chopped carbon fiber or a milled carbon fiber.
  • the amount of the fibrous filler is preferably more than 0 parts by mass and 10 parts by mass or less with respect to 100 parts by mass of the liquid crystal polymer.
  • the amount of the fibrous filler is 10 parts by mass or less, there is a tendency that the degree of warping of an outer plate to be formed decreases.
  • the liquid crystal polymer resin composition for an outer plate has sufficiently high fluidity in a planar direction and thus can be preferably used in an outer plate manufacturing method described below and shown in FIG. 2 .
  • particulate inorganic filler examples include silica, alumina, titanium oxide, boron nitride, silicon carbide, calcium carbonate, and the like are exemplary examples.
  • a measuring stabilizer As examples of the additive, a measuring stabilizer, a mold release agent, an antioxidant, a thermal stabilizer, an ultraviolet absorber, an antistatic agent, a surfactant, a flame retardant, and a colorant are exemplary examples.
  • thermoplastic resins other than the liquid crystal polymer such as polypropylene, polyamides, polyesters, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, polyetherimide, and fluorine resins; and thermosetting resins such as phenolic resins, epoxy resins, polyimide resins, and cyanate resins are exemplary examples.
  • the liquid crystal polymer resin composition for an outer plate of the present embodiment can be manufactured by mixing the liquid crystal polymer, the plate-shaped filler, and the other components that are used as necessary at the same time or in an appropriate order.
  • the liquid crystal polymer resin composition for an outer plate of the present embodiment is preferably a liquid crystal polymer resin composition for an outer plate that is pelletized by melting and kneading the liquid crystal polymer, the plate-shaped filler, and the other components that are used as necessary using an extruder.
  • An outer plate of the present embodiment is an injection molded body for which the liquid crystal polymer resin composition for an outer plate is used as a forming material.
  • vehicle exterior components and chassis of electronic goods are exemplary examples.
  • vehicle exterior components car roof components are exemplary examples.
  • chassis of electronic goods a chassis of home appliances or an electronic device chassis are exemplary examples.
  • the outer plate manufactured using the liquid crystal polymer resin composition for an outer plate of the present embodiment has an excellent sound absorption property.
  • the outer plate of the present embodiment is a vehicle exterior component and the vehicle exterior component is a component having a portion that becomes substantially horizontal with respect to the ground surface such as a bonnet or a roof, a rain sound absorption effect is strongly felt, which is preferable.
  • an outer plate (exterior component) molded using the plate-shaped molded body that is manufactured using the liquid crystal polymer resin composition for an outer plate of the present embodiment is used as an electronic goods, the vibration sounds of a motor or the wind sounds of a fan that is stored in the electronic goods are easily absorbed, which is preferable.
  • the outer plate of the present embodiment is preferably a large-sized outer plate in which the projected area of the maximum surface is 400 cm 2 or more.
  • the outer plate of the present embodiment preferably has an average thickness of 0.03 cm or more and 0.5 cm or less.
  • the ratio of the projected area of the maximum surface (unit: cm 2 ) to the average thickness (unit: cm) is preferably 8,000 or more.
  • the outer plate of the present embodiment preferably has a deflection temperature under load (DTUL) of 200°C or higher and lower than 260°C.
  • DTUL of the outer plate is 200°C or higher, in the case of applying a powder coating step after molding, the outer plate does not easily deform in the powder coating step.
  • DTUL of the outer plate is 200°C or higher, DTUL is sufficiently higher than a practical use temperature range, and the outer plate does not easily deform during practical use, which is preferable.
  • DTUL in the present embodiment, a value obtained by measuring DTUL of a test specimen obtained by pelletizing the liquid crystal polymer resin composition for an outer plate, then, drying the pellets, and injection-molding the pellets using a PS40E-5ASE-type injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd. at a load of 1.82 MPa according to ASTM D 648 was employed.
  • the test specimen was 127 mm in length, 12.7 mm in width, and 6.4 mm in thickness.
  • the outer plate of the present embodiment is manufactured by injection-molding the liquid crystal polymer resin composition for an outer plate of the present embodiment.
  • FIG. 2 is a planar pattern diagram showing the outer plate manufacturing method of the present embodiment and a planar pattern diagram showing flows of a resin at the time of molding a rectangular outer plate.
  • a gate G2 is set throughout an entire region of a side S1 of a mold M2 in a planar view.
  • the molten resin is caused to flow from the gate G2 to a side S2 that is opposite to the side S1. Therefore, a flow direction of the molten resin becomes a uniform direction from the gate G2 toward the side S2.
  • the orientation direction of the liquid crystal polymer becomes a uniform direction.
  • the outer plate manufacturing method of the present embodiment it is formed a state in which the residence of the molten resin is suppressed until the mold M2 is fully filled with the molten resin. And it is formed a state in which the molten resin flows, in the flow direction of the resin, from the side S1 to the opposite side S2 of the mold M2 at all times.
  • the orientation direction of the liquid crystal polymer becomes a uniform direction, and an internal stress generation direction is controlled to be uniform.
  • warping is reduced.
  • FIG. 3 is a schematic explanatory view of a mold that is preferably used for the manufacturing of the outer plate of the present embodiment.
  • a mold 100 shown in FIG. 3 has a cavity 110, a gate 120, a runner 130, and sprues 140.
  • the cavity 110 is a space corresponding to an outer plate to be molded.
  • the cavity 110 is a space surrounded by an inner wall of the mold 100.
  • the inner wall of the mold 100 has a shape that is complementary to an outer form of the outer plate to be molded.
  • the shape of the inner wall of the mold 100 in contact with the cavity 110 is transferred, and an outer plate having an outer form with a shape complementary to the shape of the inner wall is obtained.
  • the cavity 110 is shown to have an approximately rectangular shape in a planar view.
  • the outer plate molded in the cavity 110 can be removed by, for example, dividing the mold 100 into two (upper and lower) parts along a parting line 119.
  • the gate 120 is provided along approximately the entire width of a side 111 of the cavity 110.
  • the gate 120 needs to be provided at a location at which the flow distance in the cavity 110 of the molten resin that flows into the cavity 110 through the gate 120 becomes short.
  • the gate 120 needs to be provided at a side that becomes longest in the planar-view shape of the cavity 110.
  • the planar-view shape of the cavity 110 is identical to the projected shape of the outer plate to be molded.
  • the gate 120 along a long side and cause the molten resin to flow in a short-side direction in the mold.
  • the gate 120 is provided at the above-described location, the flow distance of the molten resin becomes short.
  • the gate 120 needs to be provided at a side that is as close to a straight line as possible.
  • the flow directions of the molten resin become similar, and the orientation directions of the resin cured in the cavity are likely to become similar.
  • the runner 130 is provided across the entire area of the gate 120 along an extension direction of the gate 120 and is connected to the gate 120.
  • the inside space of the runner 130 has a wedge-shaped portion in which the width gradually decreases toward the gate 120 in a cross section perpendicular to an extension direction of the runner 130.
  • the thinnest portion of the runner 130 is a portion that is connected to the gate 120.
  • the sprues 140 are provided at a plurality of places along the extension direction of the runner 130.
  • the extension direction of the runner 130 is identical to the extension direction of the gate 120.
  • a direction in which the resin flows into the runner 130 from the sprues 140 and a direction in which the resin flows into the cavity 110 from the runner 130 need to intersect with each other.
  • the molten resin that has been melted in an injection molding machine, not shown flows in.
  • the molten resin flows into the runner 130 through the respective sprues 140.
  • FIGS. 4 and 5 are planar pattern diagrams that show the flow of the molten resin at the time of injecting the molten resin into the mold 100.
  • white arrows represented by a reference sign R indicate the flowing molten resin.
  • the sizes of the white arrows indicate the flow amounts of the flowing resin, and a larger white arrow indicates a larger flow amount.
  • a molten resin R that is injected into the mold 100 from the injection molding machine flows as described below.
  • the molten resin R injected from the plurality of sprues 140 spreads into the inside of the runner 130.
  • the inside space of the runner 130 is designed to have a width that gradually decreases in a wedge shape and a pressure loss that gradually increases. Therefore, the molten resin R flows in a direction in which the pressure loss is smaller. That is, the molten resin R, first, flows in the extension direction of the gate 120 while filling the runner 130 instead of flowing toward the gate 120.
  • the gate direction a direction from the sprues 140 toward the gate 120 will be simply referred to as "the gate direction" in some cases.
  • the present inventors found through studies that, in runners that are connected to ordinarily-known film gates, a portion in which the molten resin injected into the runner stops is likely to be generated, the molten resin solidifies in the runner, and poor molding is likely to be caused. What has been described above will be described below.
  • the runner does not have a wedge shape. Therefore, the molten resin that flows in the gate direction receives an abrupt pressure loss when flowing into the gate from the runner. Therefore, in the case of using the film gate, first, the molten resin flows in the extension direction of the runner, and the flow of the molten resin in the gate direction is likely to stop.
  • the melt viscosity of the liquid crystal polymer highly relies on the shear velocity. Therefore, when the flow velocity of the molten resin decreases and the shear velocity decreases, the melt viscosity of the molten resin of the liquid crystal polymer abruptly increases, and the reflow of the molten resin becomes extremely difficult. In a region in which the flow of the resin stops as described above, the solidification of the resin is accelerated. Therefore, when the flow velocity of the molten resin in the gate direction decreases in the case of using the film gate, the solidification of the resin is accelerated along the gate, and the resin does not flow in the gate direction.
  • the sprues 140 are formed in a direction that intersects with both the extension direction of the gate 120 and the gate direction. Therefore, the molten resin injected from the sprues 140, first, flows to evenly spread both in the extension direction of the gate 120 and the gate direction in the runner 130.
  • the runner 130 of the mold 100 that is used in the present embodiment has a wedge shape in which the width of the inside space gradually decreases toward the gate 120. Therefore, the pressure loss that the molten resin flowing in the gate direction receives gradually increases as the width of the inside space decreases.
  • the molten resin that flows in the gate direction in the runner 130 does not reach the gate 120 within a short period of time; however, instead, the flow does not easily stop. Therefore, in the runner 130, the resin does not easily solidify during the injection of the molten resin, and the flow of the resin in the gate direction is maintained.
  • the molten resin R is not injected into the cavity 110 from the gate 120 until the runner 130 is filled.
  • the molten resin R is injected into the cavity 110 at the same time from the entire region of the gate 120. Therefore, in the cavity 110, the orientation direction of the molten resin R is likely to be determined in one direction, and it becomes easy to mold an outer plate in a state in which warping is reduced.
  • the molten resin is injected from a plurality of gates that is communicated with the cavity 110.
  • the molten resin R is injected from the gate 120 provided at one end of the cavity 110, and the molten resin R is caused to flow in one direction. Therefore, in a case where an outer plate to be molded has a large size, there is a concern that the molten resin R may be cooled and solidified until the front end (the front end portion in the flow direction) of the molten resin R that flows in the cavity 110 reaches the end portion of the cavity 110.
  • the molten resin R needs to be injected from a dot-shaped sub gate that is communicated with the cavity 110 using a mold having the sub gate.
  • FIG. 6 is a planar pattern diagram of a mold 200 having sub gates 150.
  • the mold 200 has a plurality of sub gates 150 that is communicated with the cavity 110.
  • the sub gates 150 are provided to be arrayed in the same direction as the extension direction of the gate 120 between the side 111 provided with the gate 120 and an opposite side 112.
  • the sub gates 150 may also be provided in a plurality of rows in the same array direction.
  • the plate-shaped filler that is included in the liquid crystal polymer resin composition for an outer plate suppresses the orientation of the resin, and the molten resin flows in one direction, and thus irregular orientations are suppressed. Therefore, according to the outer plate manufacturing method of the present embodiment, it is possible to manufacture an outer plate in which warping is reduced.
  • liquid crystal polymer resin composition for an outer plate having the above-described configuration it is possible to provide a new composition capable of favorably reducing the warping of an outer plate to be obtained.
  • the outer plate having the above-described configuration, the outer plate is obtained using the above-described liquid crystal polymer resin composition for an outer plate, and the warping of the outer plate is reduced.
  • liquid crystal polyesters liquid crystal polymers
  • the flow-starting temperature of the liquid crystal polyester is also referred to as the flow temperature and is a temperature at which the liquid crystal polyester exhibits a viscosity of 4,800 Pa ⁇ s (48,000 poise) when melted while increasing the temperature at a rate of 4°C/minute under a load of 9.8 MPa (100 kgf/cm 2 ) and extracted from a nozzle having an inner diameter of 1 mm and a length of 10 mm using a capillary rheometer.
  • the flow-starting temperature of the liquid crystal polymer serves as a rough indication of the molecular weight of the liquid crystal polymer (refer to Koide Naoyuki's "Synthesis, molding, and application of liquid crystal polymers", CMC Publishing Co., Ltd., June 5, 1987, p. 95 ).
  • Liquid crystal polymer resin compositions for an outer plate obtained by mixing the liquid crystal polyester, the plate-shaped filler, and the fibrous filler in proportions shown in Table 1 below were supplied to a co-rotating twin screw extruder having a screw diameter of 30 mm ("PCM-30HS" manufactured by Ikegai Corp) and pelletized by melting and kneading, thereby obtaining pellets of liquid crystal polyester compositions for an outer plate of Examples 1 and 2 and Comparative Example 1.
  • the units of numerical values in the table are "parts by mass”.
  • Example 1 Comparative Example 1 Resin 1 (RB100) - 20 - Resin 2 (S6000) 55 44 100 Resin 3 (S7000) 45 36 - Plate-shaped filler (mica) 33 36 - Fibrous filler 1 (glass fiber) - 7 43
  • FIG. 8 shows a planar view and a side view of the car roof.
  • FIG. 8(a) is the planar view
  • FIG. 8(b) is the side view.
  • the car roof corresponds to the outer plate of the present invention.
  • the units of numerical values shown in the drawing are "mm".
  • Injection molding conditions are as described below.
  • the location of a gate is as shown in FIG. 9 that corresponds to FIG. 8(a) .
  • the obtained molded bodies were evaluated as described below.
  • the pellet-shaped resin composition was dried and then injection-molded using a PS40E-5ASE-type injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd., thereby obtaining a 127 mm-long, 12.7 mm-wide, and 6.4 mm-thick test specimen.
  • the deflection temperature under load of the obtained test specimen was measured according to ASTM D 648 at a load of 1.82 MPa.
  • the molded body was placed on a flat plate with a convex portion facing upwards, the distances from the flat plate in a direction perpendicular to the flat plate were measured at 21 measurement points shown in FIG. 10 , and differences from the design were computed. In a case where the location of the measurement point moved to the opposite side of the flat plate compared with the design, a positive value was given, and, in a case where the location moved to the flat plate side compared with the design, a negative value was given.
  • the maximum warping amount was defined as the difference between the largest value in the positive direction and the largest value in the negative direction. In a case where the molded body does not warp, that is, the molded body is molded as designed, the maximum warping amount is zero.
  • Example 1 Example 2 Comparative Example 1 DTUL (°C) 245 233 284 Warping (mm) - 4.60 Not moldable
  • Liquid crystal polymer resin compositions for an outer plate obtained by mixing the liquid crystal polyester, the plate-shaped filler, and the fibrous filler in proportions shown in Table 3 below were supplied to a co-rotating twin screw extruder having a screw diameter of 30 mm ("PCM-30HS" manufactured by Ikegai Corp) and pelletized by melting and kneading, thereby obtaining pellets of Examples 3 to 7 and Comparative Example 2.
  • the units of numerical values in the table are "parts by mass”.
  • Example 3 The formulation of Example 3 is identical to that of Example 2, and the formulation of Comparative Example 2 is identical to that of Comparative Example 1.
  • Example 4 Example 5
  • Example 6 Example 7 Comparative Example 2 Comparative Example 3
  • Resin 1 (RB100) 20 35 7 11 21 - - Resin 2 (S6000) 44 65 93 89 79 100 100 Resin 3 (S7000) 36 - - - - - - - Plate-shaped filler (mica) 36 35 37 36 49 - - Fibrous filler 1 (glass fiber) 7 - 12 15 - 43 43 Fibrous filler 2 (carbon fiber) - 10 - - - - - - - -
  • FIG. 11 is a trihedral figure of the PC chassis.
  • FIG. 11(a) is a plan view
  • FIG. 11(b) is a front view
  • FIG. 11(c) is a side view.
  • the PC chassis corresponds to the outer plate in the present invention.
  • the units of numerical values shown in the drawing are "mm".
  • Injection molding conditions are as described below.
  • the location of a gate is as shown in FIG. 12 that corresponds to FIG. 11(a) .
  • FIG. 13 is an arrow cross-sectional view in a direction of a line A-A in FIG. 12 .
  • the units of numerical values shown in the drawing are "mm".
  • a portion indicated by a reference sign ⁇ corresponds to the above-described "wedge-shaped portion”.
  • the obtained molded bodies were evaluated as described below.
  • the molded body was placed on a flat plate with the bottom surface of the molded body facing the flat plate, and the heights in the thickness direction from the flat plate were measured at 25 measurement points shown in FIG. 14 .
  • the maximum warping amount of the molded body was defined as the difference between the largest value and the smallest value among the 25 points.
  • the 25 measurement points are present in a planar portion of the molded body, and, in a case where the molded body does not warp, that is, the molded body is molded as designed, warping is zero.
  • test specimens were produced by cutting out 18 cm ⁇ 9 cm pieces from the flat portions of the PC chassis molded products.
  • a test specimen was produced by cutting out a 18 cm ⁇ 9 cm piece from a 0.05 mm-thick PET sheet.
  • the obtained test specimen was held using a pair of window frame-shaped jigs as shown in FIG. 15 and screwed using bolts and nuts. Through holes into which the bolts were to be inserted were opened in advance at eight places in the test specimen.
  • a steel ball 50 manufactured by Tsubaki Nakashima Co., Ltd., SUJ2, diameter ⁇ : 6 mm
  • a steel ball 50 was dropped onto the center of a specimen 40 fixed using a jig 30 from a height of 77 cm, and sounds generated were collected using a sound collection microphone 60 installed at a location 6 cm below from the test specimen 40.
  • ao to a3 represent the amplitudes of a damped free vibration waveform shown in FIG. 17 .
  • the horizontal axis indicates the time
  • the vertical axis indicates the sound pressure.
  • the location of the origin corresponds to a point in time when the steel ball hit the test specimen.
  • Example 3 Example 4 Example 5
  • Example 6 Comparative Example 2 Comparative Example 3 DTUL (°C) 233 - - - 254 284 284 Gate location in PC chassis End End End End End & center End Warping of PC chassis (mm) 1.58 1.64 3.41 4.03 1.58 6.00
  • Reference Example ⁇ 1 ln(a 0 /a 1 ) 0.38
  • ⁇ 2 ln(a 1 /a 2 ) 0.45
  • ⁇ 3 ln(a 2 /a 3 ) 0.03
  • the molded bodies of Examples 3 to 7 has a smaller logarithm dampening rate ⁇ and a superior sound absorption effect than those measured from a PET sheet as a reference example.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
EP17881959.5A 2016-12-15 2017-12-14 Composition de résine polymère à cristaux liquides pour plaque externe et plaque externe Withdrawn EP3556807A4 (fr)

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JPWO2018110642A1 (ja) 2019-10-24
CN110291153A (zh) 2019-09-27

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